Organosiloxane ethers



organosilicon compounds.

- siloxanes of this invention.

No Drawing. Application November 14, 1956 "Serial No$622,011

4 Claims. (Cl. 260-4482) This inventionrelates to organosilicon compounds having ether linkages in the side chain.

' This application is a continuation-in-part of applicants copending application Serial No. 586,638, filed May 23,

1956, now abandoned.

This invention deals'with a modified form of an organosilicon'compound which has anoxygenated substituent'on the silicon. Due to'the oxygenated substituent the organosiloxanes of this invention possess unique properties which have not heretofore been known in Some of the compositions within the scope of this invention are Water soluble and unlike most prior water soluble organosilicon com- 7 pounds they do not hydrolyze upon standing in water In addition, the compositions of this inven-' tion have a high degree of alcohol solubility which solution.

renders them particularly useful in the cosmetic field.

It is the primary object of this invention to prepare novel organosiloxanes which areuseful as surface active agents, release agents, lubricants, antifoam agents and as cosmetic additives. Other objects and advantages will be apparent from the following description.

This invention relates to organosiloxanes having the unit formula in which R is a monvalent hydrocarbon radical, R is an alkylene radical, R" is an alkylene radical of at least 2 carbon atoms, R' is hydrogen, a saturated hydrocarbon or an aromatic hydrocarbon radical, ,n is an integer of at least 1 and a has a value from 0 to 2.

The siloxanes of this invention may be prepared by means of two basic reactions. The best method ofpreparing these siloxanes is reacting an unsaturated ether or the formula R' (OR"),,OB in which B-is an alkenyl radical, with an organosilicon compound. containing an SiH group. This reaction is best carried. out in the presence of catalysts such as organic peroxides, platinum or chloroplatinic acid. Under the influence of these catalysts the addition of the SiH to the unsaturated B group occurs to give the compositions of this invention.

The organosilicon compounds employed in this reaction can be monomeric hydrolyzable silanes of the formula alkoxy orthe like. After these silanes have been reacted with the unsaturated ether they can then be hy-j drolyzed in the conventional manner to produce the Alternatively, the -unsaturated ethers can be reacted with siloxanes containing the SiH group. In this case the siloxanes are prepared by a one-step process and no subsequenthydrolysis is needed. l

:In those caseswhere R'" is hydrogen it is preferable to block thehydroxyl group in the unsaturated ether with a triorganosiloxy group (for example, by reaction.

with a triorganohalosilane) prior to reaction with the organosilicon compound. This blocking prevents side reactions involving'the silicon bonded hydrogen or, any

silicon bonded halogen. After addition of :the unsat urated ether-tothe organosilicon compound has taken place the triorganosiloxy group can be removed 'by-h'ydrolysis to regenerate thehydroxyl group.

An alternative methodvof preparing some of the compounds of this invention is that of reacting a hydroxyalkyl organosilicon compound of the formula with an alkylene oxide at temperatures of to 150 C. in the presence ofcatalysts such as H stannic chloride and AlCl Underthese conditions reaction-of the alkylene oxide with the hydroxyl of the hydroxyalkyl takes place to produce a hydroxyether of the formula p u HO R"O RSiO 2 This method is I particularly adaptable. where R is a methylene group.

B group adds to the silicon itisconverted .to an alkylene radical of the sameunumberfof carbon atoms. g

R is 'any alkylene radical of at least 2 carbon atoms such as ethylene, propylene,.hexylene or octadecylene, and RT" can be, hydrogen or any saturated aliphatic hydrocarbon radical suchas methyl, ethyl, butyl, t-butyl or octadecyl; any saturated cycloaliphatic hydrocarbon radical such as cyclohexyl :or cyclopentyl; any aryl hydrocarbon radical such as phenyl', tolyl, naphthyl or xenyl and any 'aralkyl hydrocarbon radical such as benzyl.

Thus it can be seen that the intermediate ethers which are used in this invention .are the monoethers and di ethers of glycols and polyglycols. Specific examples of ethers of glycols which are operative herein are those of ethylene glycol, propylene glycol, hexylene glycol and octadecylene glycol. Specific examples of ethers of polyglycols which are operative herein are those of diethylene glycol, tetraethylene glycol, decaethylene glycol, tetrapropylene glycol 'anddihe'xylene glycol. Q

For the purpose of this invention thesilicon atom may be substituted with R groups. R can beany monovalent hydrocarbon radical such as alkyl radicals such as methyl, ethyl and octadecyl; cycloaliphatic radicals such as cyclohexyl and cyclo'pentyl; aryl hydrocarbon radicals such as phenyl, tolyl, xenyl and naphthyl;

.aralkyl hydrocarbon radicals such as benzyl and unsaturated aliphatic and cycloaliphati'c hydrocarbon radicompounds be prepared by reaction of an alkylene oxide t'vith the corresp'onding hydroxyalkyl silicon com-- pounddescribed above, It is to be tmderstood, however, that it is not imperative that this method be employed Patented. Aug.v 5, 1 8

iv although such a method avoids undesirable side reactions which may occur by adding an unsaturated ether to a silicon compound containing an unsaturated aliphatic hydrocarbon radical. v

This invention also "relates to copolymers containing from .1 to 99.9 mol percent siloxane units of the formula in which R', R", n, R, R and a are as above-defined and from .1 to 99.9 mol percent siloxane units of the formula ZaSiO in which Z is of the group monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals and b has an average value from 1 to 3 inclusive.

These copolymers can be prepared by the cohydrolysis of the corresponding hydrolyzable silanes of the formula in which Y is a hydrolyzable group. This hydrolysis can be carried out in the conventional manner for cohydrolyzing hydrolyzable silanes. Alternatively, the copolymers of this invention can be prepared directly by reacting the above-defined unsaturated ethers with copolymers containing silicon bonded hydrogen in some of the siloxane units. This reaction is carried out in an identical manner as described above.

The copolymers of this invention can contain the following types of siloxane units: ZSiO Z SiO, Z SiO and limited amounts of SiO units. For the purpose of this invention Z can be any monovalent hydrocarbon radical such as alkyl radicals such as methyl, ethyl, hexyl and octadecyl; alkenyl radicals such as vinyl, allyl and hexenyl; cycloaliphatic radicals such as cyclohexyl, cyclopentyl and cyclohexenyl; aralkyl hydrocarbon radicals such as benzyl and aryl hydrocarbon radicals such as phenyl, tolyl, 'xenyl and naphthyl. Z can also be any halogenated hydrocarbon radical such as chloromethyl, tetrafluoroethyl, trifluorovinyl, tetrafluorocyclobutyl, chlorodifluorovinyl, m,u,ottrifluorotolyl, bromophenyl and tetrabromoxenyl.

The compositions of this invention are unique in their properties because they have in the molecule both a hydrophilic and a hydrophobic portion. As a result when the hydrophilic portion is present in sufficient amount the materials are water soluble. In general it has been found that the compositions of this invention are water soluble even when as much as mol percent of the total siloxane units are of the formula Alcohol solubility is obtained with much higher percentages of the latter siloxane units. Because of the dual nature of the molecules of the compositions of this invention they are useful for emulsifying agents and for antifoaming agents.

In addition the water solubility of these materials renders them particularly useful for release agents. Prior to this invention organosilicon release agents were sold primarily in the form of aqueous emulsions. Emulsions tend to break from one cause or another and consequently are not as satisfactory as aqueous solutions. Prior to this invention the only satisfactory siloxane release agents in the water soluble class were those in which the Water solubilizing group was hydrcvlyzable. As a result when these were placed in solution and allowed to stand the siloxane invariably oiled out due to the hydrolysis of the solubilizing; group. This of .heated at C. for 48 minutes.

'4 course prevents any widespread commercial use of this type of material.

The present materials, however, are water soluble but do not hydrolyze on standing because the solubilizing group is connected to the silicon by a silicon-carbon linkage which is stable to hydrolysis. Thus the materials of this invention avoid the difficulties which have been encountered with previously known siloxane release agents.

In addition the siloxanes of this invention, both homopolymers and copolymers, are useful as lubricants and give far superior lubricity to conventional siloxanes.

The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.

Example 1 Of (hereinafter referred to as polyglycol A) was reacted with 130.2 g. of trimethylchlorosilane by heating a mixture of the two for 2 hours to a temperature of 88 C.

This was done to block the hydroxyl groups with trimethylsiloxy groups.

The resulting product was mixed with 2 g. of a 1% ethanol solution of chloroplatinic acid and 60.1 g. of a trirnethyl end-blocked methylhydrogensiloxane having a viscosity of about 20 CS. The mixture was heated at 151 C. until the solution became homogeneous. It was then cooled to C. and heated for an additional hour.

The product was then mixed with 16.3 g. of 5% hydrochloric acid and heated at from 106 to 124 C. for 1 hour to remove the trimethylsiloxy groups from the glycol side chain. The product was neutralized with sodium bicarbonate, filtered and then stripped by heating at 50 C. at 13 mm. to remove low boiling products.

The resulting product had a viscosity at 25 C. of 204 cs., an 11 of 1.4595 and a freezing point of 1 C. This material had the formula Me SiO [Si ],SiMe;

This material was water soluble and was a good antifoam agent for ethylene glycol antifreeze solutions.

Example 2 509 g. of polyglycol A and 129 g. of dimethyldichlorosilane were heated at 102 C. for 30 minutes. 2 g. of a 1% ethanol solution of chloroplatinic acid and 60.1 g. of (MeHSiO) were then added and the mixture was The product was hydrolyzed by heating with aqueous HCl and then neutralized with sodium bicarbonate and filtered. The resulting product was heated at 50 C. at 13 mm. to remove the dimethylsiloxane formed during the hydrolysis. The resulting product was heated at 50 C. at 13 mm. to re move the dimethylsiloxane formed during the hydrolysis. The resulting fluid had a viscosity at 25 C. of 455 cs., an n of 1.4555 and a freezing point of 1 C. and had the unit formula a O MeSi(CH2)a0 (CH2CH20)B.HO CHzCHaOH This material was useful as an antifoam agent for trimethylchlorosilane and refluxed 2 hours at 55 to 67 C. The product was mixed with 1 g. of a 1% ethanol solution of chloroplatinic acid, 200 cc. of dry toluene and 135.3 g. of

Ph HMeaSIO S10 SiMegH The mixture was heated at 81 to 100 C. for V2 hour.

. The excess trimethylchlorosilane and some toluene-weref and the following propertiesz viscosity at 25. of

removed by distillation and 38 g. of 2% HClwa's added. 43.8 cs. and an n of 1.4095. to the residue. The mixture was heatedat 95 to 110 Exam le 7 C. for 11 /2 hours. The material was then stripped by p heating up to 177 C. and the residue was neutralized, When 1 mol of the vinylmethylether of ethylene glycol Wi h Sodium bicarbonate, filtered .and further heated is reacted with 1 mol of trichlorosilane in the presence of to 102 C. at 3 mm. pressure. The residuehad a viscosity 1 gof a 35% dimethyl Cafhitol' Solutiollof chloroplaat 25 C. of 69 es, and a fra ti i d f 1,4541, tinic acid at a temperature of 125 C. in an autoclave for This materialhad the formula 4 hours and the resulting product is hydrolyzed, a resinous Example 4 polysiloxane of the unit formula V A mixture of 320.4 g. of the ethylvinylether of di- MeOCH CH OCH CH SiO ethylene glycol, 200 ml. of toluene, 134.3 g .;of tetramethylis obtained. a disiloxane and l g. of a 1% ethanolsolution of chloro- Example 8 platinic acid was refluxed at 90 to 117 C. for 8 hours. The resulting product was distilled to give the compound When the methylvmylethel of ethylene glycol 18 acted with phenyldichlorosilane in accordance with the M v [EtO(OHzCHzOhCHzCHzSifiQ procedure of Example 7 and the resulting product is hyboiling 170 to 171 0. at .4 mm. and having the followimlyzei fimd slloxane the formula I ing properties, a specific gravity at '25 C. of .963, a 13 viscosity at 0. of 6.82 es. and aIrn of 1.4337. 25 Meocflcfiocfiqmslo This fluid was tested on a Shell-four-ball wear tester 15 Obtainedemploying 52100 standard steel balls at 275 F..at 1200 Example 9 R. P. M. When the load was 4kg. the scar diameter was .77 mm. When the load was 40 kg. the scar diwhen an eqmmolar fixture of amfterhwis .913 This shows f lirsuperior lubricit CH2:CHCHZO(CH2CH2O)MSiMe3 at e lg 0a 0 conven 10ml S1 oxanes' and ethyldichlorosilane is heated at 120 C. for four Example 5 hours in the presence of 1 g. of a solution of 37 f the-vinylmethylether f Ethylene glycol was chloroplatinic acid in diethylcarbitol, the compound mixed with 200 ml. of toluene, 201.5 g. of tetramethyldi- 35 siloxane and 1 g. of a 1% ethanol solution of chloroplatinic acid and heated at 84 to 92 C. foi- 7 hours. The is obtained. resulting product was distilled to give 200 g. of the When 50 mol percent of this chlorosilane is 'ecohycompound 7 drolyzed with 10 mol percent monomethyltrichlorosilane,

' M 40 10 mol percent chlorophenyltrichlorosilane, 10 mol ermefooHzoHzofjHgofifsfho cent monovinyltrichlorosilaneand 20 mol percent plinhaVlHg the follOWlhg Propertles? 130111112 P01nt yltn'chlorosilane, a resinous siloxane having the composiat 1 mm, specific gravity at 25 C. of 0.945, viscosity at tion 5 mol percent 25 C. of 3.4 cs. and an n of 1.4299. I V Et Exampl 6 m0olznornjeeo oiamsio A mixture of 223 g. of the monoallylether'of diethylene glycol and 54.3 g. of trimethylchlorosilaue was heated 10 {1101 P z= 3/2 and 20 mol Percent at 58-68 C. for 2 /2 hours. .The'product was mixed s/z 1S Obtalhedzvithull30 g. of a siloxane of the average molecular Example 10 orm a Me2 Me2 I The following slloxanes are obtained when the follow- Hsimsiohmsm ingethers are: reacted with tetramethyldisiloxane in acml. of toluene and 1 g, of a .35 dimethyl-carbitol H cordance with the procedure of Example 4.

10 mol per cent MeSiO3 10 mol percent ClC I-I Si0 solution of chloroplatinic acid and heated at 93 to 106.5 Example 11 C. for'6 hours. Some of the toluene and the excess when 1 mol of h I ydroxypropylvlnylslloxane is reacted g gi g gg g gi gsg sg' 3 Si 7; with 1 mol of ethylene oxide by heating a mixture of were en a e an e 1 W s v the two at 120 c. in the presence of 1 g. of 1101., a

hours at 95 C. The remaining toluene and water were 7 fl eha v1n the rut formula distilled off, the product neutralized Wlth sodium brcar- S1 Oxan H OH CH bonate, filtered and then stripped by heating to C. HO(CHz)2O(CH2)sSiO at 1.5 mm. The resulting product had the average is Obtainei molecular formula Example 12 M62 M82 M82 75 H(0 CHsCHzlz (OHr)a [0 ]z1.0S1(OHm HZ D A m1xture of 196.8 g. of the allylmethylether of ethyl- 7 ene glycol, 96.2 g. of a 25 cs. trimethyl end blocked cordance with the procedure of Example 13, the followmethylhydrogenp olysiloxane fluid, 200 ml. of dry ing products are obtained.

Glycol Ether Siloxane Product Mes M92 Me: Me: CHz=CHCH2O(CHgCHzOhSiMe; CnHmSiOSiH CmHuSlOSiCHzCHgCHzO(CH CHzOMH M82 M82 Me: Me: CH2=CHCH20(CHgCHzO)zSiMG3 OwHasSiOSlH CmHaaSgOSlOHQCHgCHzO(CHZCH20)2H M8 N162 M62 Me:

toluene and 3 g. of a solution of chloroplatinic acid in the dimethyl ether of diethylene glycol, said solution containing .14% by weight Pt, was heated at 109 to 118 C. for 4 hours and 21 minutes. The product was then heated to 215 C. at 2 mm. to remove low boiling materials. The residue was a fluid of 3000 cs. viscosity at 25 C. having an index of refraction of 1.4481 at 25 C. This fluid had the formula CHZCHQCHZO OHzCHzOMe MeaSiOQ {iO ],SiMe;

Example 13 A mixture of 588 g. of

CH =CHCH O CH CH O) H and 162.9 g. of Me SiCl was heated for 4 hours and inutes at from 67 to 102 C. The product was cooled to room temperature and 210.4 g. of PhMe SiOSiMe H, 4 g. of the platinum catalyst of Example 12 and 400 ml. of toluene were added. The resulting mixture Was heated at 92 to 118 C. for 7 hours. The unreacted Me SiCl and toluene were removed and the product was hydrolyzed with 27 g. of 2% HCl solution by heating at 95 C. for 2 hours. The product was neutralized with NaHCO cooled and filtered. The product was heated to 107 C. at 2 mm. to remove volatile materials. The residue was a fluid having the formula N162 PhMGzSiOSiCHzCHzCHzO (CHzCHzO)i2H and the following properties: viscosity 40 cs. at 25 C. and n 1.4605. This material was a good emulsifying agent for aqueous emulsions of phenylmethyl siloxanes.

Example 14 When the following glycol ethers are reacted with the That which is claimed is l. A siloxane of the unit formula in which R is a monovalent hydrocarbon radical, R is an alkylene radical, R is an alkylene radical of at least 2 carbon atoms, 11 is an integer of at least 2, R' is selected from the group consisting of hydrogen, saturated hydrocarbon radicals and aryl hydrocarbon radicals and a has a value from O to 2 inclusive and from .1 to 99.9 mol percent siloxane units of the formula ztsi0 in which Z is selected from the group consisting of monovalent hydrocarbon radicals and halogenated mono valent hydrocarbon radicals and b has an average value from 1 to 3 inclusive.

4. A copolymer in accordance with claim 3 in which following siloxanes and the product hydrolyzed in acboth R and Z are methyl radicals.

References Cited in the file of this patent UNITED STATES PATENTS 2,476,307 Klein et a1. July 19, 1949 2,584,751 Speier Feb. 5, 1952 2,721,873 MacKenzie et al. Oct. 25, 1955 FOREIGN PATENTS 1,118,495 France Mar. 19, 1956 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,846,458 August 5, 1958 Loren A Haluska It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns '7 and 8, in the table, third column thereof, the second product should read as shown below instead of as in the patent aM e 0 H siosicH cH cH 0(021 011 9} H,,

Signed and sealed this 4th day of November 1958.

Attest:

KARL H... AXLINE Attesting Oflicer ROBERT C. WATSON Commissioner of Patents UNITED STATES PATENT swish CERTIFICATE @F CURREQTFEQN Patent No, 2,846,458 August 5, 1958 Loren Aa Haluska It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns '7 and 8, in the table, third column thereof, the second product should read as shown below instead of as in the patent in MegMg G l-l' SiOSiCH CI-LGE G(CH CH Q H Signed and sealed this 4th day of November 1958,

(SEAL) Attest:

KARL MINE ROBERT c. WATSON Attesting Oflicer Commissioner of Patents 

1. A SILOXANE OF THE UNIT FORMULA
 3. A COPOLYMERIC SILOXANE COMPOSED OF FROM .1 TO 99.9 MOL PERCENT SILOXANE UNITS OF THE FORMULA 